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Several silsesquioxanes have found to be sensitive to nucleophilic attack. For example see: (a) Feher, F. J.; Budzichowski, T. A.; Rahimian, K.; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3859. (b) Feher, F. J.; Rahimian, K.; Budzichowski, T. A.; Ziller, J. W. Organometallics 1995, 14, 3920. (c) Day, V. W.; Klemperer, W. G.; Mainz, V. V.; Millar, D. M. J. Am. Chem. Soc. 1985, 707, 8262.
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Several silsesquioxanes have found to be sensitive to nucleophilic attack. For example see: (a) Feher, F. J.; Budzichowski, T. A.; Rahimian, K.; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3859. (b) Feher, F. J.; Rahimian, K.; Budzichowski, T. A.; Ziller, J. W. Organometallics 1995, 14, 3920. (c) Day, V. W.; Klemperer, W. G.; Mainz, V. V.; Millar, D. M. J. Am. Chem. Soc. 1985, 707, 8262.
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Introduction of bulky trimethylsilyl substituants on the cyclopentadienyl liganda significantly improved the selectivity of the reactions.
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62
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Poor crystallinity is a general characteristic of silsesquioxane compounds: (a) Feher, F. J. J. Am. Chem. Soc. 1986, 108, 3850. (b) Feher, F. J.; Budzichowski, T. A.; Ziller, J. W. Inorg. Chem. 1992, 31, 5100. (c) Buys, I. E.; Hambley, T. W.; Houlton, D. J.; Maschmeyer, T.; Masters, A. F.; Smith, A. K. J. Mol. Catal. 1994, 86, 309.
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85034544472
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2MgCl) of the chloride complexes 6-9 did not afford well-defined products.
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For example, see: (a) Bochmann, M.; Lancaster, S. J,; Hurst-house, M. B.; Malik, K. M. A. Organometallics 1994, 13, 2235 and references therein, (b) Horton, A. D.; de With, J.; van der Linden, A. J.; van de Weg, H. Organometallics 1996, 15, 2672. (c) Pellecchia, C.; Immirzi, A.; Grassi, A.; Zambelli, A. Organometallics 1993, 12, 4473.
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85034559512
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note
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Conditions: 20 mmol of MAO; 20 μmol of catalyst; 5 atm of ethylene, 80°C, 7 min. Observed activities range between 0.4 and 1.2 kg of PE/ (mmol[cat] h atm), based on the polymer yield after 7 min.
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3N/MAO are known styrene polymerization catalysts, indicating that Ti-O bonds can be split by MAO: (a) Chien, J. C. W.; Salajka, Z. J. Polym. Sci., Part A: Polym. Chem. 1991, 29, 1253. (b) Kim, Y.; Hong, E.; Lee, M. H.; Kim, J.; Han, Y.; Do, Y. Organometallics 1999, 18, 36.
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3N/MAO are known styrene polymerization catalysts, indicating that Ti-O bonds can be split by MAO: (a) Chien, J. C. W.; Salajka, Z. J. Polym. Sci., Part A: Polym. Chem. 1991, 29, 1253. (b) Kim, Y.; Hong, E.; Lee, M. H.; Kim, J.; Han, Y.; Do, Y. Organometallics 1999, 18, 36.
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(b) Buys, I. E.; Hambley, T. W.; Houlton, D. J.; Maschmeyer, T.; Masters, A. F.; Smith, A. K. J. Mol. Catal. 1994, 86, 309.
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85
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85034564248
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8) were not very informative, as broad signals were observed at both -45 and +25°C.
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85034553335
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To reduce DFT calculation time, the silsesquioxane cyclopentyl substituents were replaced by hydrogens.
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100
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